Siwei Zhao, Hongyi Wang, Gang Fu, Wenqing Zhen, Meiling Liu, Li Yang* and Jiaxu Zhang*,
{"title":"反应动力学驱动的E2/SN2选择性。卤素键合洞察","authors":"Siwei Zhao, Hongyi Wang, Gang Fu, Wenqing Zhen, Meiling Liu, Li Yang* and Jiaxu Zhang*, ","doi":"10.1021/prechem.3c00053","DOIUrl":null,"url":null,"abstract":"<p >Ubiquitous competition of stereospecific E2 elimination versus S<sub>N</sub>2 substitution is of central importance in chemical synthesis. Herein, we uncover how the nature of the leaving group affects the intrinsic competing dynamics that remains largely unknown as opposed to its role in reactivity. Results are presented for a prototype case of fluoride anion reacting with ethyl chloride, compared to reacting with ethyl iodide. Chemical dynamics simulations reproduce scattering signatures observed in experiments and reveal that the direct stripping/rebound mechanisms characterize the E2/S<sub>N</sub>2 reactions, in line with their dynamic fingerprints identified. Quite similar structures and energetics are found for the Cl<sup>–</sup> and I<sup>–</sup> leaving halides, whereas the competing dynamics show markedly distinct features. A halogen-bonding attraction is found to be crucial that modifies the interaction potential in the entrance channel and essentially tunes the underlying atomistic behaviors causing a mechanistic shift. This work highlights the dynamical effects induced by a leaving group on the proceedings of base-induced elimination and nucleophilic substitution, providing a unique insight into the reaction selectivity for complex chemical networks and environments.</p>","PeriodicalId":29793,"journal":{"name":"Precision Chemistry","volume":null,"pages":null},"PeriodicalIF":0.0000,"publicationDate":"2023-08-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/prechem.3c00053","citationCount":"1","resultStr":"{\"title\":\"E2/SN2 Selectivity Driven by Reaction Dynamics. Insight into Halogen Bonding\",\"authors\":\"Siwei Zhao, Hongyi Wang, Gang Fu, Wenqing Zhen, Meiling Liu, Li Yang* and Jiaxu Zhang*, \",\"doi\":\"10.1021/prechem.3c00053\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Ubiquitous competition of stereospecific E2 elimination versus S<sub>N</sub>2 substitution is of central importance in chemical synthesis. Herein, we uncover how the nature of the leaving group affects the intrinsic competing dynamics that remains largely unknown as opposed to its role in reactivity. Results are presented for a prototype case of fluoride anion reacting with ethyl chloride, compared to reacting with ethyl iodide. Chemical dynamics simulations reproduce scattering signatures observed in experiments and reveal that the direct stripping/rebound mechanisms characterize the E2/S<sub>N</sub>2 reactions, in line with their dynamic fingerprints identified. Quite similar structures and energetics are found for the Cl<sup>–</sup> and I<sup>–</sup> leaving halides, whereas the competing dynamics show markedly distinct features. A halogen-bonding attraction is found to be crucial that modifies the interaction potential in the entrance channel and essentially tunes the underlying atomistic behaviors causing a mechanistic shift. This work highlights the dynamical effects induced by a leaving group on the proceedings of base-induced elimination and nucleophilic substitution, providing a unique insight into the reaction selectivity for complex chemical networks and environments.</p>\",\"PeriodicalId\":29793,\"journal\":{\"name\":\"Precision Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":0.0000,\"publicationDate\":\"2023-08-10\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/epdf/10.1021/prechem.3c00053\",\"citationCount\":\"1\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Precision Chemistry\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/prechem.3c00053\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"\",\"JCRName\":\"\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Precision Chemistry","FirstCategoryId":"1085","ListUrlMain":"https://pubs.acs.org/doi/10.1021/prechem.3c00053","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
E2/SN2 Selectivity Driven by Reaction Dynamics. Insight into Halogen Bonding
Ubiquitous competition of stereospecific E2 elimination versus SN2 substitution is of central importance in chemical synthesis. Herein, we uncover how the nature of the leaving group affects the intrinsic competing dynamics that remains largely unknown as opposed to its role in reactivity. Results are presented for a prototype case of fluoride anion reacting with ethyl chloride, compared to reacting with ethyl iodide. Chemical dynamics simulations reproduce scattering signatures observed in experiments and reveal that the direct stripping/rebound mechanisms characterize the E2/SN2 reactions, in line with their dynamic fingerprints identified. Quite similar structures and energetics are found for the Cl– and I– leaving halides, whereas the competing dynamics show markedly distinct features. A halogen-bonding attraction is found to be crucial that modifies the interaction potential in the entrance channel and essentially tunes the underlying atomistic behaviors causing a mechanistic shift. This work highlights the dynamical effects induced by a leaving group on the proceedings of base-induced elimination and nucleophilic substitution, providing a unique insight into the reaction selectivity for complex chemical networks and environments.
期刊介绍:
Chemical research focused on precision enables more controllable predictable and accurate outcomes which in turn drive innovation in measurement science sustainable materials information materials personalized medicines energy environmental science and countless other fields requiring chemical insights.Precision Chemistry provides a unique and highly focused publishing venue for fundamental applied and interdisciplinary research aiming to achieve precision calculation design synthesis manipulation measurement and manufacturing. It is committed to bringing together researchers from across the chemical sciences and the related scientific areas to showcase original research and critical reviews of exceptional quality significance and interest to the broad chemistry and scientific community.